Acid dyestuff of the anthraquinone series



ratemeu v. na wee wraith:Ii v srurss PATENT/OFFICE r 1,935,929 sore measure or ran ANTHRAQUINONE 1 SERIES Karl Zahn and Heinrich Koch, Frankfort-onthe-llilain-lfiochst, Germany, assignors to General Aniline Works, Inc, New York, N. Yz, a. corporation of Delaware No Drawing. Application December 23, 1932,

' Serial No. 648,731, and in-Germany J 6 Claims.

The present invention relates to acid dyestuffs of the anthraquinone series, more particularly it relates to valuable dyestuffs having'the followin generalfonnulm,

. SO H wherein Rstands for an unsubstituted or substituted aromatic radical and R1 for an alkyl radical or for a substituted alkyl radical, such as alkyl,OH. alkyl-COOH, or alky1-.-COO. v alkyl,

the grouping -i-sOz-ehu stendingin one of the positions meta, and narain relation'to the group,

Our new dyestuffs are obtainable by causing 1- amino-4-halogenanthraquinone-2-su1fonic acid good levelling power and dye the animal'ilber from an acid bath blue tints. U

It is surprising that the metaand para-aminoaryl-alkyl-sulfones undergo the said condensation reaction with 4-lialogen-1-an1ino-2-sulfonic acid or a salt thereof in subh ah easy manner, since, as we have found, theortho-amino-arylalkylsullones could not be condensed with the said halogen-anthraquinone sulionic acid compound.

The present invention includesthe freedyestuff-sulfonic acids and, of course, the salts thereof.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weighty l b (1) 4D partsoi! the sodium salt oi 1-amino-4- bromo-anthraquinone-Z-sulionic acid are heated ,for several hours attic C. to'ioi- CrWi-fll :parts or meta-ammophenyl-metbylsulfoue 200 parts or a salt thereof, such as an alkali metal salt, to

tints of good tastness properties, for instance, of

armory-- of water in the presence of 10 parts of sodium bicarbonate and 1 part of cuprous chloride, until the formation of the dyestuff is finished. The difficultly soluble sodium salt of the dyestuff thus formed can easily be isolated. The dyestufi is purified by re-dissolving it in water'and again salting out by means of sodium chloride. In the dry state it forms a blue powder and dyes wool from anacid-bath clear blue tints of very good levelling power. The dyestuff has the following structural formula: A;

SOECH: By using instead of meta-aminophenyl-niethylsulfone the corresponding -ethylsulfone a blue dyestufl. of similar properties is obtained. In like manner other meta-amino-pheriyl-alkylsuliontes containing other alkyl groups may be used.

(Z) By using instead 01"25 parts 1 of metaaminophenyl-methylsulfone 25 parts of para aminophenyl-methylsulfone' and by effecting the condensation at C. to 0., there is likewise obtained a blue dyestuff which dyes wool from an acid bath clear blue tints and. which corresponds to the formula:

(3) 32 parts of the sodium salt of meta-aminophenylsulfone acetic acid are heated to gently boiling for several hours with 40 parts 01 the sodium salt of 1-amino-4-bromo-anthraqulnone- 2-sulionic acid, 80 parts of a sodium carbonate solution of 10% strength, 1 part of cuprous chloride and 120 parts of water. The blue dyestull thus formed is precipitated by acidifying the solution with dilute hydrochloric acid.

It has the fol lowing formula:

feoonkcoon The dyestuff acid thus obtained may be transto the following formula:

I OI NEE "[7 v SUSHI X 0 NH 5 sOi-cm-w'oocm '36 In like manner other alkylesters, such as the methylor propyl-ester may be formed.

Both dyestuifsthe free dyestufi acid as well as its esterdye Wool clear blue tints of good fastness properties. g i

(4) 40 parts of the sodium salt 'of l-aminolbromo-anthraquinone-2-su1fonio acid are heated for several hours at C. to C. with 32 parts of 5-amino-2-acetylaminophenyl-methy1sulfone (melting at 197 C. to 198 C.; obtainable from 2-acetyl-amino-pheny1methylsulfone by nitration and subsequent reduction), 40 parts of sodium carbonate solution of 10% strength, 20 parts of sodium-bicarbonate and 1 part of cuprous chloride in 240. parts of water. The dyestufi which the usual manner; it dyes wool l'eddish blue tints of very good levelling power. Itcorresponds formed into its ethylester by means of ethylalc o i hol and gaseous hydrochloric acid; it'corresponds has separated in a crystallineform, is purified in and of similar dyeing properties is obtained if instead of 32 parts of 5-amino-2-o,oety1mninophenyl-mcthylsulfone 32 parts of 5-emino-2- chloro-phenylmethylsulfone ere usedl j "Inariaiialogous manner the dyestuif: 30

soifi SOT-CH3 is-formed [by using 32 parts of 5-amiiro-2- methyl-phenyl-methylsulfone Other metoa or pera-amino-phenylelkysul fones containing other substituerrts in the phenyl radical or being substituted in the alkyl radical 300 may be used in an analogous manner.

(5) 26 parts of meta-eminophenyl-hyd1'0xyethylsul'fone, 40 parts of the sodium salt of l amino-4 bromo-anthraquinone 2-su1fonic acid, I 16 parts of sodium-bicarbonate and 1 part of I65 cuprous chloride are heated in 150 parts of water forseveral hours at 60 C'. to 70 C. The dyestufl precipitates in the course of the con densation in the form of smellbrilliant crystals. In the dry state it forms a. blue powder dyeing fit) wool from an acid' 'bath clear blue tints. The dyestuff has the following formula:

-'- BOPCHn-GHr-OH By using 26 parts; of pera-aminophenyl-hy droxyethylsulfone (meltingst 107 C. to 108C.) instead of metaamino-phenyl-hydroxy-ethylsulfone, adyestuff of similer properties is obtamedivhic h th ufql e s or ula: no

5:! i I i he [4 l sokdr'n-om-on' Dyestuffs containing higher hydroxyalkyl radicals attached to the S02 group mayalsobe formed' (6-) 40 parts of the sodium salt of bamino-- -bromo-anthrequinone-2-sulfonicz;. acid, 321 parts 2&0

wherein R stands for a radical of the benzene or 2 amino tetra hydro-5.l.7.8-naphthy1-4- methylsulfone (melting at 129 C. to 131 0.), 20 parts of sodium-bicarbonate and 1 part of cuprous chloride are heated for 643 hours at '70" C. to C. in 200 parts of Water. The dyestuff precipitates in a crystalline form with a.

very good yield. It dyes wool from an acid bath clear reddish-bluetints. The dyestufl corresponds to the following formula:

sour

/CH2\ 0 NH CH2 SOz-CH;

Dyestufis having properties similar to those of the dyestuffs described in the before-mentioned examples are obtained by using components which are analogous to those disclosed in the specific examples.

We claim:

1. Acid dyestuffs dyeing animal fiber from an acid bath blue tints and corresponding to the general formula:

wherein R stands for an aromatic radical and R1 for an alkyl radical, the grouping -SO2-R1 standing in one of the positions meta and para in relation to the NH group.

2. Acid dyestuffs dyeing animal fiber from an acid bath blue tints and corresponding to the general formula: 1

SOaH

series and X represents hydrogen, --OH, --COOI-I acid bath blue tints and corresponding to the general formula:

' chem-x I wherein X stands for hydrogen, alkyl, -COOH, -COO--alkyl or CH2--OH and Y for hydrogen, -CH3, --C1 or -NI-I--COCH3.

4. The acid dyestuff dyeing animal fiber from an acid bath clear blue tints of good fastness properties and corresponding to the formula:

SOz-Clh 5. The acid dyestuif dyeing animal fiber from an acid bath clear blue tints of good fastnessproperties and corresponding to the formula:

SOIH

S Oa-GHi-CHa-OH 6. The acid dyestuff dyeing animal fibers from an acid bath clear blue tints of good fastness properties and corresponding to the formula:

or --COO-alkyl, the grouping ----SOz---a1ky1ene.X

standing in one of the positions meta and para in relation to the'-NH- -group.

3.-Acid dyestuffs dyeing animal fiber from an BOr-OHr-COO-CaHs KARL ZAHN. HEINRICH KOCH. 

